Rubbery diene polymer composition containing an oxidized polymer of butadiene



United States Patent 0 RUBBERY DlENE POIiYM ER COMPOSITION CON- TAINING AN OXlDIZED POLYMER 0F BUTA- DIENE William M. Hutchinson, Bartlesville, Okla, assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application Sept. 4, 1956, Ser. No. 607,556, which is a continuation of application Ser. No. 308,520, Sept. 8, 1952, now Patent No. 2,959,619, dated Nov. 8, 1960. Divided and this application Sept. 8, 1958, Ser.

7 Claims. (Cl. 260-313) This is a division of my copending application Serial No. 607,556, filed September 4, 1956, now Patent 2,959,- 619, dated November 8, 1960, which was a continuation of application Serial No. 308,520, filed September 8, 1952, now abandoned.

This invention relates to novel compositions of matter, i.e., oxygenated polymeric products. In a further aspect this invention relates to a process for oxidizing polymeric materials and subsequently deperoxidizing these materials to provide novel oxygenated products. In a further aspect this invention relates to a process for oxidizing polymeric materials and hydrogenating the oxidized material to provide oxidized-hydrogenated polymeric materials.

I have discovered that polymeric materials and more especially liquid polymeric materials, such as liquid polybutadiene, can be oxidized and then, if desired, hydrogenated. This oxidation is carried out at elevated temperatures in the presence of a catalyst by contacting these liquid polymers, dissolved or dispersed in a solvent, with a free oxygen containing gas. Following oxidation, the oxidized material can be deperoxidized. Either before or after this deperoxidation step the oxidized material can be hydrogenated.

Each of the following objects is attained by at least one of the aspects of this invention.

An object of this invention is to provide novel oxygenated polymeric products and to provide a process for \preparing these products. A further object of this invenion is to provide novel oxygenated-hydrogenated poly- Igneric products. A further object of this invention is to provide liquid oxidized-hydrogenated polymeric materials {which are resistant to further oxidation. A further object of this invention is to provide novel products which can be employed as rubber softeners, components of coating compositions, tackifiers, and the like.

Further objects and advantages of this invention will be apparent to one skilled in the art upon reading this specification.

According to the process of the present invention a suitable liquid polymer or copolymer, such as liquid polybutadiene, having a viscosity in the range of 100 to 6000 Saybolt Furol seconds at 100 F. is dissolved or dispersed in an inert solvent, such as toluene, and charged to an oxidation reactor fitted with agitation means to provide complete contacting of the polymer solution or dispersion and oxidant during the oxidation reaction. The reactor is then closed and oxygen, or a suitable free oxygen containing gas such as air, is bubbled through the solution with heating and agitation for a period of 2 to 90 hours. In said oxidation an initiator such as an organic peroxide 3 ,035,025 latnted May 22, 1962 ice or hydroperoxide is frequently employed to start the reaction. When the oxidation has been terminated the product can be subject to thermal treatment while in liquid phase at about oxidation reaction temperature to destroy peroxide groups. The product So produced can be employed as a rubber softener, a component of a coating composition, tackifier, and the like.

In a further step in accordance with the process of my invention, the oxidation efiluent described above, either before or after deperoxidation, is charged to a hydrogenation reactor for further treatment. If necessary, the oxidation etlluent may be diluted with an additional quantity of solvent to lower its viscosity and thereby to provide improved contacting -in the hydrogenation zone. Accordingly, the oxidation efiluent is charged to the hydrogen-ator and a small amount of hydrogenation catalyst, such as palladium-on-charcoal or the like, is admixed therewith and the reactor is purged of air. Hydrogenation is then effected at a temperature in the range of 70 to 400 F. and with a pressure in the range of 30 to 4000 p.s.i.g. for a period of 2 minutes to 50 hours.

The products of the present invention contain from a fraction of 1% to 15% by Weight of oxygen, more often 4 to 9% by weight of oxygen. The oxygen introduced into these materials is present in the form of carbonyl oxygen and as hydroxyl oxygen. The oxygenated products are further characterized by viscosities in the range from 300 to 10,000 Saybolt Furol seconds as measured at 100 F. and hydroxyl numbers in the range from 10 to 250 mg. of potassium hydroxide per gram of product.

In the oxygenated-hydrogenated materials, carbonyl oxygen is partially converted to hydroxyl oxygen and at least a portion of the remaining unsaturation in the molecule is saturated with hydrogen. The hydrogenated products are characterized by a lack of skinning when exposed to the atmosphere. Oxygenated-hydrogenated polymeric products are produced which contain from a fraction of 1% to 15% by weight of oxygen, said oxygen being present in the form of carbonylic oxygen and hydroxyl oxygen. These products are especially useful as softeners for elastorners.

Polymeric materials applicable for use as starting materials in the preparation of my novel products include liquid polymers of conjugated dienes and liquid copolymers of conjugated dienes with compounds containing an active CH =C group. The liquid polymers applicable for use in this invention can be prepared by any polymerization method, such as mass or emulsion polymerization, conducted in such manner that liquid polymers are formed. One such method comprises polymerizing di' olefins or cyclodiolefins such as 1,3-butadiene, isoprene, 1,3-cyclopentadiene, 1,3-cyclohexadiene and the like in the presence of a catalyst, for example, anhydrous hydrogen fluoride dissolved in an aliphatic polyfluoro com pound such as 1,1-difiuoroethane. Particularly adaptable are liquid polymers of butadiene prepared according to the method of Patent 2,631,175 of W. W. Crouch filed December 23, 1948, wherein 1,3-butadiene is polymerized in the presence of an alkali metal catalyst such as finely divided sodium, and a suitable diluent such as xylene. Suitable comonomers for the monomeric materials disclosed above include styrene, alkyl, substituted styrenes, acrylonitrile, ethyl acryla't'e, methyl acrylate, methyl methacrylate and others known in the art. The liquid polymeric starting materials used in the present invention are characterized by having viscosities in the range from 100 to 6,000 Saybolt Furol seconds at 100 F. Reaction conditions in the oxidation zone include temperatures in the range from 125 to 375 F., preferably 150 to 290 F., and atmospheric pressures are usually satisfactory althoug-h higher pressures are employed to maintain liquid phase conditions to prevent loss of solvent, where a low-boiling solvent is used. The length of the oxidation period varies depending upon the degree of oxidation desired, but is usually in the range from 2 to 90 hours, preferably 4 to hours. I prefer to conduct the oxidation in such manner as to provide an oxidate having an oxygen content in the range from approximately 4 to 9 weight percent of oxygen. Oxidation initiators known in the art can be employed, if desired, to start theoxidation reaction. Materials which are free radical generators under the conditions employed are used for this purpose. These include organic peroxides and hydroperoxides such as benzoyl peroxide, acetyl peroxide, d-iisopropylbenzene hydroperoxide [dimethyl(isopropylphenyl) hydroperoxymethane], tert butylisopropyl-benzene hydroperoxide [dimethyl(tert-butylphenyl)hydroperoxymethane], isopropylbenzene hydroperoxide [dimethyl(phenyl)-hydroperoxyrnethane], and the like. The amount of initiator employed will be in the range of 0.1 to 10 weight percent of the polymeric material being oxidized.

Hydrogenation conditions include temperatures in the range from 70 to 400 F., preferably from 90 to 300 F. Any suitable pressure within the capacity of the hydrogenator can be employed with pressures from about to 4000 p.s.i.g. providing a convenient operating range. The length of the hydrogenation will be in the range from 2 minutes to hours, preferably from 10 minutes to 2 hours. dium, cobalt, platinum and the like either supported or unsupported. Catalysts such as copper chromite, molybdenum sulfide or others of similar nature, while less preferred, can also be employed.

Solvents for the starting materials include those materials which are substantially inert .to oxidation or hydrogenation under the conditions employed. In the oxidation step it is desirable to employ a solvent to prevent gelation of the reaction mixture. in the oxidation and hydrogenation steps include straight chain hydrocarbons containing from 6 to 10 carbon atoms, aromatic hydrocarbons such as benzene, toluene, xylene and the like, dioxane, isopropyl alcohol carbon tetrachloride and others.

The novel materials produced in the present invention are useful as additives forelastomers such as rubber, resinous materials such as polyvinyl chloride and the like. They are also useful as adhesives, painter varnish components, etc.

Example 1 A charge comprising 50 grams of sodium-polymerized liquid polybutadiene having a viscosity of 488 Saybolt Furol seconds at 100 R, 0.5 gram of hydroperoxide initiator and 500 grams of carbon tetrachloride was placed in a reactor provided with stirring means and a tube for the introduction of oxygen just above the stirrer. Upon completion of charging, the reactantmixture was 1 Soltrol 140 hydroperoxide 41 wt. percent hydroperoxide in the parent hydrocarbon). oltrol 140 is an isoparatfimc hydrocarbon fraction boiling in the range from 365 to 410 Fl t-prepared by catalytic alkylation of parafiins with monoo e 115, 7

Suitable catalysts include palladium, nickel, rho- Solvents suitable for use both heated to a temperature of 155-160 F. and oxidation was started. Excess oxygen was bubbled through the rapidly stirred mixture at the aforementioned temperature for a period of 24 hours. At the end of this period oxygen was cut ofi and the reaction mixture thereafter held at 155 to 160 F. for approximately 6 hours to decompose peroxidic materials. At this point a sample of the oxidation product was soluble in normal heptane and insoluble in acetone. The product was stripped of solvent and dried in air for 15 hours at 212 F. Before drying the stripped product was fluid at 140 F. and stiff at room temperature (70 F.) After drying the material had set to a soft gel. The product was soluble in acetone and had a carbon content of 79.5 weight percent, hydrogen content of 10.2 weight percent and oxygen by difference of 9.1 weight percent. The product had a hydroxyl number of 161 mg. KOH/ g. sample.

Example 11 A charge comprising 410 grams of sodium polymerized liquid polybutadiene having a viscosity of 435 Saybolt Furol seconds at 100 PK, 2000 grams of toluene, and 5 grams of curnene hydroperoxide was placed in a reactor provided with a stirrer and a tube for the introduction of oxygen just above the stirrer. Upon completion of charging, the temperature was raised to 203 F. and oxidation was started. Excess oxygen Was bubbled through the rapidly stirred reaction mixture at a temperature in the range from 199 to 205 F. for a period of 8.25 hours. At the end of this period oxygen Was cut off and the reaction mixture was held at 230 F. for approximately 16 hours to decompose peroxidic materials.

Solvent was then removed by fractionation to recover the product. The product had a carbon content of 83.26 weight percent, a hydrogen content of 10.24 weight percent and an oxygen content (by difference) of 6.48 weight butadiene-styrene elastomer.

percent.

This product was evaluated as a 'plasticizer in a tire tread recipe using a 41 F., Mooney (ML-4), 71/29 Stocks were compounded using the following recipe:

, Parts by weight 41 F. GR-S (butadiene-styrene rubber) 100.0 Philblaek O #5 a 50.0

Zinc oxide 3.0

Stearic acid u 1.0 Flexamine 1.0 Sulfur 1.75

Santocure 1.00 Softener 10.0

1 High abrasion furnace black.

'A physical mixture, containing percent of a complex drarylammeketone reaction product and 35 percent of N,N'- drphenyl-p-phenylenediamiue.

A rubber accelerator. A condensation product of mercaptobenzothiazole with cyclohexylumine. A light tan or buffcolored powder; M.P. C. (min.) sp. gr. 1.27.

The compounded stocks were milled and cured for 30 minutes at 307 F. and physical properties of each vulcanizate determined. A control was run using a blend of equal parts of Paraflux (an asphaltic flux) and Circosol- ZXH (a petroleum hydrocarbon softener containing hydrocarbons of high molecular weight in the form of a heavy, viscous, transparent, pale green, odorless liquid of low volatility; sp. gr. 0.904; Saybolt viscosity at F Analysis showed 1.? weight percent-chlorine (from sol- 0 vent).

F., about 2000 seconds). The following evaluation data were obtained:

pressure of 1200 to 1040 pounds per square inch gage, approximately 0.44 mole of hydrogen had been adsorbed. Approximately 95 percent of the hydrogen adsorption was oxygenated o effected during the first 37 minutes of o eration. At this p a gg figgg 5 point the catalyst was removed by filtration and the diene filtrate stripped of solvent at from 100 to 200 F. and

from 100 to 2 mm. mercury pressure. Unaged Samples: Q The product obtained from the above operation was ggfiggg gg ggg gffi f it 670 1 180 medium brown in color and was tacky. It did not skin Tensile psi 3,200 3,520 when exposed to the atmosphere for 6 days at 158 F. stregsgg a ifi'fibggggi gbbj 'fiS''Efiii 700 600 The product had a hydroxyl number 0f 90 mg. g. cure sample when analyzed by the acetic anhydride-pyridine ar at at method ys eresls, l I t sih ep ce ercent 341 The above product was evaluated as a softener for a g g g -t t .2353 2:5; 74/216 1,3-b1itad1eneaEryloni tIr li11e tcolpoly mer prepareddlby ompress1onse,percen emu $1011 0 merlza on. B O OWlH com 0111] 'n compounded MS 1% 43.5 red 6 i 1 ed g p g itii ii iii/1 2 3 2 as p p y P b h 0 cs nue 5. arts y weig t g gg q ffff I g 1,3-butadiene-acrylonitrile copolymer 100 O AlziRg il geze ro i zg -5o.5 51.5 2 Philblack A 60.0

ven ge OUISS .I

Stressstrain properties at 80 F. Zmc oxlde 1 5100 Pfircent Modulns,p.s.i $.278 g, Altax 1.5

ens e, p.s.i 5 Elongation, percen 530 435 Steal-1c n g s resi a'rfi Sulfur 1.5

ES 161108, percen .1 Flex Life, 29.0 9.9 2v Softener Shore 65 62 Medium abrasion furnace black.

Example III A charge comprising 600 grams of sodium-polymerized liquid polybutadiene having a viscosity of 435 Saybolt Benzothiazyl disulfide.

The samples were compounded and cured at 307 F. for 30 minutes. The results obtained were recorded in the 30 following table.

Percent Softener Oom- Percent e Percent Phr b 300% Tensile,. Percent pression swelled Extracted Softener Modulus, p.s.i. Elonga- S p.s.i. tion oxygenated Polybutadiene 10 1, 360 2, 440 465 13. 5 52. 5 2.8 T d 10 1, 590 2, 840 440 15.0 33.6 4. s Dihutylphthalate 10 1, 380 2, 560 460 15. 0 38. 6 4. 7

OVEN AGED 24 HOURS AT 212 F.

oxygenated Polybutadiene 10 0 420 330 TP-90B 10 2, 670 3,060 380 Dibutylphthalate 10 2, 440 3, 180 380 B minute cures used on aged stress-strain tests.

b Phr-pnrts per 100 parts of rubber.

1! Seven days in 70/30 isooctane-toluene mixture, 45 minutes cure.

d TP-QOB, a well known polyether of high molecular we ght generally employedinlow temperature plasti izafion, as a control or reference for evaluation of new plasticizer materials.

Furol seconds at 100 F., 9 grams of cumene hydroperoxide, and 1200 grams of toluene, was placed in a reactor provided with stirring means and a tube for the introduc- :tion of oxygen just above the stirrer. Upon completion of charging, the temperature of the reactants was raised to 5.

203 F. and oxidation begun. Excess oxygen was bubbled through the rapidly stirred mixture at a temperature in the range of 200 to 205 F. for a period of 88%. hours. At the end of this period oxygen feed was stopped and the reaction mixture was thereafter held at 0 203 F. for approximately 16 hours to decompose peroxidic oxidation products. The reaction mixture was then treated with decoloring charcoal and Celite 3 filteraid and filtered.

To 250 ml. of the above filtrate was added 250 ml. of a 6 -50 mixture of dioxane and isopropyl alcohol. One gram of 10 percent palladium-on-charcoal catalyst (21 commercial preparation comprised of about 10 weight percent palladium on activated charcoal) was then added and the mixture charged to a hydrogenator. After 28 7 hours at a temperature of 85 to 94 F. and a hydrogen 3 A filter aid made from exceptionally pure, inert, diatomaceous silica (Celite) of fine pore size; especially adapted for removing slimy or colloidal material from filtrations of semivlscous or non-viscous liquids. Comparable in use but more uniform in particle size than infusorial earth (kieselguhr).

The test data show that oxygenated-hydrogenated liquid polybutadiene of the present invention provides compounded rubber stocks of good tensile strength. The test data further show that oxygenated-hydrogenated liquid polybutadiene is more resistant to extraction than TP-90B.

The product was also evaluated as a plasticizer in a tread recipe using a 41 F., Mooney (ML4), 71/29 butadiene-styrene elastomer. Stocks were compounded using the following recipe:

1 High abrasion furnace black.

0 A physical mixture containing percent of a complex diarylaruine-ketone reaction product and 35 percent of N,N'- diphenyl-p-phenylenediamine.

A rubber accelerator. A condensation product of merca%tobenzothiazole with cyclohexylamine. A light tan or bu -co1ored powder; M.P. -194 F. (min); sp. gr. 1.27.

The compounded stocks were milled and cured for 30 minutes at 307 F. and physical properties of each vulcanizate determined. A control was run using a blend of equal parts of Paraflux (an asphalt-ic flux) with Circo sol-2XH (a petroleum hydrocarbon softener containing hydrocarbons of high molecular weight in the form of heavy, viscous, transparent, pale green, odorless liquid 5 polymer having been prepared by hydrogenating an oxyof low volatility; sp. gr. 0:940; Saybolt viscosity at 100 genated polymer selected from the group consisting of F., about 2000 seconds). The following evaluation data homopolymers of butadieue and copolymers of butadiene were obtained. with compounds containing an active CH =C group, said oxidized polymer containing up to 15 percent oxygen by Weight, said oxygen being present in the form of car-' oxygenated Cireosolbonylic oxygen and hydroxyl oxygen, and having a visilgigf g izgg cosity of 300 to 10,000 Saybolt Furol seconds at 100 F. butadiene and a hydroxyl number of l0 to 250 mg. of potassium hydroxide per gram of saidoxygenated polymer, said Unaged damplesi hydrogenation being effected by mixing said oxygenated ggfi iz gfggg gig gi L070 17170 polymer with an inert solvent, contacting the resulting Tensile psi 3,430 3, 560 mixture with hydrogen in the presence of a catalyst at a glga ggfi ggig F 45 mihitemperature of 70 to 400 F. under a pressure of 30 to cure a 4000 p.s.1.g., and recovering the thus treated polymer.

gfiig fg k a'g" gfg 2?; 5. The composition of claim 4 wherein said rubber is Resilence, Percent 53.8 61.5 selected from the group consisting of butadiene/styrene 5g 2 and butadiene/acrylonitrile copolymers. Compression seEFrceriE 18.6 17.9 6. The composition of claim 4 wherein said rubber is gggggggggii gfigf 4&5 a butadiene/acrylonitrile copolymer.

lncheshninutmn 40.3 40.1 7. As a new composition of matter, rubbery diene polyfig ggjgggfig 102 rner and, as a softener therefor, a compound selected Ida 250 25 from the group consisting of (1) an oxidized polymer z isgj gggg a' 245 35 selected from the group consisting of homopolymers of Stress-strain roperties at 80 15.- butadiene and copolymers of butadrene with compounds gtlglnlsieigcegrg IiModulus, p.s.1 23% gg containing an active CH =C group, said oxidized poly- Elon aiior' 'fiirlii .1111: 400 '42s mer containing up to 15 percent oxygen by weight, said ggfi iggij' g fi' gag 23:? oxygen being present in the form of carbonylic oxygen Flex Lite,'M -i 14. 7 10.7 and hydroxyl oxygen, said oxidized polymer having been Share Harduessm- 65 60 prepared by mixing a liquid polymer selected from the group consisting of homopolymers of butadiene and copolymers of butadiene with compounds containing an These data show that the softener of the present rnvenactive CH2=C group with a Solvent, contacting Sal-d tion provides tread stocks of improved tack and aged mixture with f oxygen containing gas at a temps? flex f ature in the range of 125 to 375 F., stopping the flow As Flanyfosslble emhodlmems may be made of 'm of said oxygen containing gas, maintaining said elevated Invention wlthout departing from the scope thereof, it is {empemmre for a period of time to decompose peroxide to be understood that all matter herein set forth is to be groups, recovering the oxidized Polymer and (2) a hydro interpreted as illustrative and not in a limiting sense. 'genated oxygenated polymer Selected from the group com 91mm: 7 -sisting of homopolyrners of butadiene and copolymers of AS a 313W compesmon of marten q '5jbutadiene with compounds containinganactive CH ==C polymer and, as a softener therefor, an oxidized polymer 7 VgToupJ hi Polymer having been prepared hydrogenatselected from the group consisting of homopolymers of mg an oxygenated polymer salected from the group com butadlene and coPolyme'rs of butadlene Y sqmpounds sisting of homopolymers of butadiene and copolymers of containing}? actlve. CHECK group Sald butadiene with compounds containing an active CH =C contalnmg to Permt oxygen by i Sad group, said oxidized polymer containing up to 15 percent 071378511 being vPresant the of Carbonyl? Oxygen oxygen by weight, said oxygen being present in the form and hydroxyl-oxygen, said oxidlzed polymer having been of carbonyhc oxygen and hydroxyl oxygen and having piepared y {mxmg a hqmd polymer from the a viscosity of 300 to 10,000 Saybolt Furol seconds at 100 group conslstmg t m e of butadlene, a F. and a hydroxyl number of 10 to 250 mg. of potassium, polymers of butadiene w th compounds contannng an hydroxide per gram of said oxygenated polymer Same active CH =C group with an Inert solvent, contacting hydrogenation being effected by mixing Said oxygenatedgj said mixture with a free Pxygen contammg gas polymer with a solvent, contacting the resulting mixture 1 in range 0t to 375 with hydrogen in the presence'of a catalyst at a temperflow of said oxygen contammg m,amta1mng sald ature of 70 to 400? F. under a pressure of 30 to 4000 vated temperature for a period of time to decompose ps'hgq and recovering the thus e d l peroxide groups,'reco=vering the oxidized polymer. V

2; h composition of claim 1 wherein said rubber References Cited in the file of this patent selectedfrom the group consisting of butadiene/ styrene UNITED STATES PATENTS and butadiene/acryloni trile'copolymers.

3. The composition of claim 1 "wherein said rubber is 2,638,460 Crouch May 12, 1953 la butadiene/styrene copolymer. 2,692,892 H 1lyer et a1 Oct. 26, 1954 )4. As a new composition of matter, rubbery diene poly- 2,842,513 Fitzgerald .et a1. July 8, 1958 mer and, as a softener therefor, a hydrogenated oxygenated polymer selected from the group consisting of homopolymers of butadiene and copolymers of butadiene with compounds containing an active CH =C group, said 

7. AS A NEW COMPOSITION OF MATTER, RUBBERY DIENE POLYMER AND, AS A SOFTENER THEREFOR, A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) AN OXIDIZED POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF BUTADIENE AND COPOLYMERS OF BUTADIENE WITH COMPOUNDS CONTAINING AN ACTIVE CH2=C< GROUP, SAID OXIDIZED POLYMER CONTAINING UP TO 15 PERCENT OXYGEN BY WEIGHT, SAID OXYGEN BEING PRESENT IN THE FORM OF CARBONYLIC OXYGEN AND HYDROXYL OXYGEN, SAID OXIDIZED POLYMER HAVING BEEN PREPARED BY MIXING A LIQUID POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF BUTADIENE AND COPOLYMERS OF BUTADIENE WITH COMPOUNDS CONTAINING AN ACTIVE CH2=C< GROUP WITH A SOLVENT, CONTACTING SAID MIXTURE WITH A FREE OXYGEN CONTAINING GAS AT A TEMPERATURE IN THE RANGE OF 125* TO 375*F., STOPPING THE FLOW OF SAID OXYGEN CONTAINING GAS, MAINTAINING SAID ELEVATED TEMPERATURE FOR A PERIOD OF TIME TO DECOMPOSE PEROXIDE GROUPS, RECOVERING THE OXIDIZED POLYMER, AND (2) A HYDROGENATED OXYGENATED POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF BUTADIENE AND COPOLYMERS OF BUTADIENE WITH COMPOUNDS CONTAINING AN ACTIVE CH2=C< GROUP, SAID POLYMER HAVING BEEN PREPARED BY HYDROGENATING AN OXYGENATED POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF BUTADIENE AND COPOLYMERS OF BUTADIENE WITH COMPOUNDS CONTAINING AN ACTIVE CH2=C< GROUP, SAID OXIDIZED POLYMER CONTAINING UP TO 15 PERCENT OXYGEN BY WEIGHT, SAID OXYGEN BEING PRESENT IN THE FORM OF CARBONYLIC OXYGEN AND HYDROXYL OXYGEN, AND HAVING A VISCOSITY OF 300 TO 10,000 SAYBOLT FUROL SECONDS AT 100* F. AND A HYDROXYL NUMBER OF 10 TO 250 MG. OF POTASSIUM HYDROXIDE PER GRAM OF SAID OXYGENATED POLYMER, SAID HYDROGENATION BEING EFFECTED BY MIXING SAID OXYGENATED POLYMER WITH A SOLVENT, CONTACTING THE RESULTING MIXTURE WITH HYDROGEN IN THE PRESENCE OF A CATALYST AT A TEMPERATURE OF 70 TO 400*F. UNDER A PRESSURE OF 30 TO 4000 P.S.I.G., AND RECOVERING THE THUS TREATED POLYMER. 